Pentachloroethanesulfenyl chloride and chlorination process for producing same



United States Patent 3 259 653 PENTACHLOROETHANESULFENYL CHLORIDE AND CHLORINATION PROCESS FOR PRO- DUCING SAME Edward D. Weil, Lewiston, Emil J. Gearing, Grand Island, and Keith J. Smith, Lockport, N .Y., assignors to Hooker Chemical Corporation, Niagara Falls, N.Y., a corporation of New York No Drawing. Filed Nov. 30, 1962, Ser. No. 241,184

3 Claims. (Cl. 260-543) In accordance with this invention it has been found that pentachloroethanesulfenyl chloride may be produced by chlorination of CCl =CClSCl, which is the subject of co-pending application S.N. 852,931, filed in the US. Patent Office on November 16, 1959, of which application the present application is a continuation-in-part.

This invention relates to pentachloroethanesulfenyl chloride and a method for the manufacture thereof.

Chlorination of CCl =CClSCl may be conducted by reacting gaseous or liquid chloride or equivalent chlorinating agent with liquid CCl ==CClSCl at suitable temperatures in the range of about ---40 degrees to about 150 degrees centrigrade. At lower temperatures, the reaction is sluggish; at higher temperatures some decomposition occurs. As to reaction pressure, atmospheric pressure is suitable and subatmospheric pressures may also be employed but a superatmospheric pressure reaction has the advantage of improved reaction rates. Although the reaction proceeds, albeit slowly, without a catalyst, it is decidedly advantageous to employ a suitable catalyst. Among these are Lewis acids, such as ferric chloride, antimony chloride, iodine (converted in situ to iodine chloride); chlorosulfonic acid, and the like. Light also functions as a catalyst. Especially effective are light rays of shorter wave-length, such as those emitted by a mercury vapor lamp.

The reaction is run until the desired weight uptake occurs. The product obtained is purifiable by sublimation and/or by recrystallization, preferably from an inert solvent such as hexane.

Another synthesis is by the substitutive chlorination of tetrachloroethanesulfenyl chloride (which is the subject of copending patent application S.N. 800,981, filed in the US. Patent Ofiice on March 23, 1959, now abandoned). This chlorination, which proceeds very slowly without a catalyst, may be conducted at a satifactory rate by use of a strong organic acid catalyst of the type which is acidic to Congo red indicator. Examples of suitable catalysts include trichloroacetic acid, trifiuoroacetic acid, tetrachloroethanesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and ethyl hydrogen sulfate. Temperatures in the range of 40 degrees to 150 degrees may be conveniently employed. In place of chlorine, other suitable chlorinating agents, such as sulfuryl chloride and sulfur dichloride, may be used in either of the processes outlined above. Reaction times for the above reactions are usually within the range of 4 hours to 72 hours, depending on temperatures employed and other factors. Also, the weight of a chemical catalyst may usually be from about 0.1 to percent by weight of the material to be chlorinated. Furthermore, other lower polychloroethanesulfenyl chlorides may be chlorinated to the pentachloroethanesulfenyl chloride by similar procedures.

The product of the invention is a yellowish crystalline solid, soluble in most of the ordinary organic solvents, and having a characteristic pungent odor. It can be sublimed under vacuum without decomposition. In contrast, to trichloromethanesulfenyl chloride, the product exhibits a notable degree of pesticidal activity per se, and also utility as a chemical intermediate. It is particularly active as a nematocide and fungicide, andmay be used for combination effect crop protection. By pesti- 3,259,653 Patented July 5, 1966 "ice.

cidal it is meant that the product is fungicidal, nematocidal and antibacterial. It is particularly effective against soil pathogens, such as fungi, nematodes, and soil bacteria and destroys them when applied to the soil or loci thereof.

The present compound may be used in pure form or may be formulated with other materials. Suitable formulations include solutions in organic solvents with or without surface-active agents to facilitate dispersion in water. Suitable solvents include aromatic and aliphatic hydrocarbons such as xylenes and naphthas, chlorinated solvents such as carbon tetrachloride, and brominated solvents such as ethylenedibromide. Pentachloroethanesulfenyl chloride may also be formulated with solid carriers, either powders or granules, such as clay, talc, vermiculite, sawdust, ground corn cobs, and the like. In liquid preparations from /2 to percent by weight of pentachloroethanesulfenyl chloride is preferably employed and in dispersion on solid carriers from /2 to percent is found most useful. Synthetic surface active agent present, usually an organic anionic or nonionic wetting agent of the lower alkylene oxide (nonionic) or sulfonated type (anionic), may be in proportion of .1 to 20 percent of the final product.

As a chemical intermediate, pentachloroethanesulfenyl chloride may be reacted .with nucleophiles such as salts of imides, cyanide, thiocyanate, sulfide, mercaptides, phosphites, and the like, to replace the chlorine atom attached to the sulfur by the nucleophilic groups employed.

The following examples are given to illustrate the invention but are not to be considered as limitations thereof.

All parts given in the examples, specification and claims are by weight, and all temperatures are in degrees centigrade, unless other wise indicated.

Example 1.Preparation of pentachloroethanesuljenyl chloride by chlorination of trichloroethylenesulfenyl chloride with gaseous chlorine Into a mixture of 1 gram of anhydrous FeCl and 19.8 grams trichloroethylenesulfenyl chloride at room temperature was passed a stream of chlorine. The tempera- .ture was allowed to rise to degrees centigrade. As the chlorination neared completion, the temperature dropped to room temperature. The gain in weight was the theoretical 7.1 grams. The reaction mixture was gently warmed and filtered to remove inorganic solids, then stripped free of low boiling contaminants by warming to 73 degrees centigrade at 0.1 millimeter of mercury. At this point, the product began to sublime. The sublirnate was a yellowish pungent solid, with a melting point of 78 degrees centigrade. It analyzed 79.2'percent Cl and 11.1 percent S, compared to a calculated chlorine content of 79.1 percent and sulfur content of 11.9 percent. The infrared spectrum analysis showed the product to be free of carbon-to-carbon double bonds, thus confirming the structure.

Example 2.Preparation of penmchloroethanesulfenyl chloride by chlorination of trichloro-ethylenesulfenyl chloride with liquid chlorine 19.8 grams of trichloroethylenesulfenyl chloride were added to 213 grams of liquid chlorine at its boiling point (about 33 degrees centigrade) in an open Dewar flask in the presence of ferric chloride, and the chlorine was allowed to evaporate ofi slowly. To the residual solid was added enough carbon tetrachloride to dissolve the organic crystals and the ferric chloride was removed by filtration. The carbon tetrachloride was evaporated and the residual mixture of liquid and crystalline solid was stripped to 50 degrees centigrade at l millimeter of mercury pressure. The undistilled residue comprised a yellowish crystalline solid, having the properties and analysis of the product described in Example 1.

Example 3.Preparation f penlachloroethanesulfenyl chloride by catalytic chlorination 0f tetrachloroetlzanesulfenyl chloride Into a mixture of 100 parts of tetrachloroethanesulfenyl chloride (produced as described in co-pending application S.N. 800,981) and 2 parts of trichloroacetic acid catalyst was passed a stream of chlorine at 25-30 centigrade for 2 days. The weight increase was substantially the theoretical for monochlorination. The product, a yellowish solid mass, was shown by infrared and gas chromatography to be identical to the product of Example 1.

Example 4.Use as a foliar fungicide Tomato plants inoculated with spores of Alternaria solani were sprayed with an 0.04 percent aqueous dispersion of pentachloroethanesulfenyl chloride. Similar inoculated plants were left unsprayed. Two weeks later, when severe symptoms of early blight disease were observed on the inoculated unsprayed plants, the sprayed plants were substantially disease free.

Example 5 .Urc as a soil fungicide Soil heavily infested with damping-off organisms, notably Pythium fungi, was admixed with pentachloroethanesulfenyl chloride at a concentration of 50 parts per million. Peas planted in the treated soil germinated and emerged normally, whereas peas planted in the same soil without the chemical treatment damped off and failed to emerge.

Example 6.Use as a nematocide Soil heavily infested with nematodes (Metoidogyne incognita) was admixed with pentachloroethanesulfenyl chloride at 125 parts of chemical per million parts of soil. Cucumber seedlings planted in this treated soil showed substantially less damage from root knotting caused by nematodes than did similar seedlings planted in the same soil without the chemical treatment.

Example 7 .-Pesticidal formulation A formulation suitable for use as a nematocide was prepared by blending the following:

Parts Pentachloroethanesulfenyl chloride 10 Mineral spirits 90 Example 8.Pesticidal formulation A wettable powder formulation suitable for pesticidal use was prepared by grinding together the following ingradients in a hammar mill:

Parts Pentachloroethanesulfenyl chloride 50 Naphthalenesulfonate wetting agent (Sorbit P) 3 Ligninsulfonate dispersing agent (Marasperse N) 6 Synthetic clay (Microcel E) 41 chloride which comprises chlorinating tetrachloroethanesulfenyl chloride with a chlorinating agent at a temperature between about 40 centigrade and centigrade in the presence of a catalyst of trichloroacetic acid.

3. A method for producing pentachloroethanesulfenyl chloride which comprises treating tetrachloroethanesulfenyl chloride with a chlorinating agent at a temperature between about minus forty degrees centigrade and 150 degrees centigrade in the presence of a catalyst of trifiuoroacetic acid.

References Cited by the Examiner UNITED STATES PATENTS 2,774,707 12/ 1956 Birum 260543 2,824,136 2/1958 Ospenson 260543 2,898,261 8/1959 Youngson 167-22 2,944,080 7/1960 Johnston 260543 3,088,818 5/1963 Geering 260543 3,095,350 6/1963 Earhart et al. 16722 3,144,482 8/1964 Flay 260543 3,144,483 8/1964 Flay 260-543 OTHER REFERENCES Houben-Weyl: Methoden der Organischen Chemie, vol. 5, part 3, 1962, pp. 529532.

LORRAINE A. WEINBERGER, Primary Examiner. LEON ZITVER, Examiner.

B. M. EISEN, H. C. WEGNER, Assistant Examiners. 

1. PENTACHLOROETHANESULFENYL CHLORIDE
 2. A METHOD FOR PRODUCING PENTACHLOROETHANESULFENYL CHLORIDE WHICH COMPRISES CHLORINATING TETRACHLOROETHANESULFENYL CHLORIDE WITH A CHLORINATING AGENT AT A TEMPERATURE BETWEEN ABOUT -40* CENTIGRADE AND 150* CENTIGRADE IN THE PRESENCE OF A CATALYST OF TRICHLOROACETIC ACID. 